US5668066A - Near infrared absorption filter glass - Google Patents
Near infrared absorption filter glass Download PDFInfo
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- US5668066A US5668066A US08/685,572 US68557296A US5668066A US 5668066 A US5668066 A US 5668066A US 68557296 A US68557296 A US 68557296A US 5668066 A US5668066 A US 5668066A
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- United States
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- near infrared
- infrared absorption
- absorption filter
- glass
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- 239000011521 glass Substances 0.000 title claims abstract description 109
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 41
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- 150000001342 alkaline earth metals Chemical group 0.000 claims abstract description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 16
- 229910016997 As2 O3 Inorganic materials 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- 229910052706 scandium Inorganic materials 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 23
- 229910011763 Li2 O Inorganic materials 0.000 abstract description 8
- 229910004742 Na2 O Inorganic materials 0.000 abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 5
- 239000010452 phosphate Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 41
- 239000000126 substance Substances 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 22
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 14
- 230000008025 crystallization Effects 0.000 description 14
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 12
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 12
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 229910052681 coesite Inorganic materials 0.000 description 11
- 229910052906 cristobalite Inorganic materials 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 229910052682 stishovite Inorganic materials 0.000 description 11
- 229910052905 tridymite Inorganic materials 0.000 description 11
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 9
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 8
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 8
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 8
- 229910018404 Al2 O3 Inorganic materials 0.000 description 7
- 238000004031 devitrification Methods 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 229910004446 Ta2 O5 Inorganic materials 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910016264 Bi2 O3 Inorganic materials 0.000 description 5
- 229910005230 Ga2 O3 Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 4
- 229910019639 Nb2 O5 Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 4
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 4
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 4
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 4
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910017895 Sb2 O3 Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- -1 Cu+ ion Chemical class 0.000 description 1
- 229910003944 H3 PO4 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- VUDJAFZYSMINQA-UHFFFAOYSA-L zinc metaphosphate Chemical compound [Zn+2].[O-]P(=O)=O.[O-]P(=O)=O VUDJAFZYSMINQA-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0085—Compositions for glass with special properties for UV-transmitting glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S501/00—Compositions: ceramic
- Y10S501/90—Optical glass, e.g. silent on refractive index and/or ABBE number
- Y10S501/904—Infrared transmitting or absorbing
Definitions
- the present invention relates to near infrared absorption filter glass, more specifically to filter glass which has spectral characteristics that it highly transmits light having a wavelength of 400 to 600 nm and selectively absorbs near infrared light having a wavelength greater than about 600 nm, and which is used particularly for the color correction for a color VTR camera.
- JP-A-62-128943 discloses colored glass formed of 60 ⁇ 90% by weight of P 2 O 5 , 7.5 ⁇ 20% by weight of Al 2 O 3 , 0 ⁇ 15% by weight of B 2 O 3 +SiO 2 , 1 ⁇ 25% by weight of BaO+CaO+SrO, 0 ⁇ 15% by weight of Y 2 O 3 +La 2 O 3 +ZrO 2 +Ta 2 O 5 +TiO 2 , 0 ⁇ 10% by weight of PbO and 0.4 ⁇ 15.0% by weight of CuO.
- JP-A-4-104918 discloses phosphate glass formed of 60 ⁇ 80% by weight of P 2 O 5 , 3 ⁇ 11% by weight of Al 2 O 3 , 3 ⁇ 9% by weight of BaO, 3 ⁇ 20% by weight of MgO+CaO+BaO+SrO, 1 ⁇ 5.5% by weight of Li 2 O, 1 ⁇ 10% by weight of Li 2 O+Na 2 O+K 2 O, 0 ⁇ 5% by weight of SiO 2 +B 2 O 3 , 0 ⁇ 5% by weight of ZrO 2 +TiO 2 +Y 2 O 3 +La 2 O 3 and 0.2 ⁇ 10% by weight of CuO.
- the present inventors have made diligent studies to overcome the above problems, and as a result have found that, when it is attempted to obtain phosphate-based near infrared absorption glass containing CuO, there can be obtained glass which has high transmittance characteristics at 400 ⁇ 600 nm and sharp absorption characteristics at a wavelength greater than 600 nm, useful as a near infrared absorption filter, and which has a small thermal expansion coefficient and excellent chemical durability, by adding a relatively large amount of ZnO and a proper amount of alkali metal oxides to a composition containing 35-50% of P 2 O 5 .
- the present invention has been made on the basis of the above finding, and the gist thereof is a near infrared absorption filter glass comprising
- FIG. 1 shows transmittance curves of glass obtained in Examples 3 and 4 and Comparative Example 3.
- the near infrared absorption filter glass of the present invention comprises 35 ⁇ 50% of P 2 O 5 , 0 ⁇ 5% of Li 2 O, 0 ⁇ 12% of Na 2 O, 0 ⁇ 20% of K 2 O, 0 ⁇ 20% of Cs 2 O, 1.5 ⁇ 20% of R 2 O (in which R is an alkali metal), 17 ⁇ 48% of ZnO and 0.2 ⁇ 12% of CuO.
- P 2 O 5 is the most preferred glass network-forming component for increasing the transmittance at 400 ⁇ 600 nm and sharply changing the absorption by Cu 2+ in a wavelength region greater than 700 nm.
- the content thereof is less than 35%, no desired transmittance characteristic is obtained, and further, it is difficult to stably produce the glass since the crystallization tendency of the glass increases.
- the above content exceeds 50%, the glass shows a sharp decrease in chemical durability, and the glass intended in the present invention is no longer obtained. Therefore, the amount range of P 2 O 5 in composition is limited to 35 ⁇ 50%.
- the amount range of P 2 O 5 is preferably 37 ⁇ 49%, particularly preferably 40 ⁇ 48%.
- K 2 O is a component for improving devitrification resistance and improving the melting properties of glass.
- the amount thereof is greater than 20%, the glass is poor in chemical durability and has an increased thermal expansion coefficient.
- the amount range of K 2 O in composition is therefore limited to 0 ⁇ 20%, and it is preferably 0 ⁇ 17%.
- the near infrared absorption filter glass of the present invention may contain Li 2 O, Na 2 O and Cs 2 O as alkali metal oxides as required in addition to the above K 2 O.
- Li 2 O, Na 2 O and Cs 2 O are components for improving the melting properties of the glass and improving devitrification resistance. When the amounts of these components exceed 5%, 12% or 20%, the glass is poor in chemical durability, or the crystallization tendency is intensified. Therefore, the amount range of Li 2 O in composition is limited to 0 ⁇ 5%, the amount range of Na 2 O in composition is limited to 0 ⁇ 12%, and the amount range of Cs 2 O in composition is limited to 0 ⁇ 20%.
- the amount range of Li 2 O is preferably 0 ⁇ 3%, the amount range of Na 2 O is preferably 0 ⁇ 8%, particularly preferably 0 ⁇ 6%, and the amount range of Cs 2 O is preferably 0 ⁇ 17%, particularly preferably 0 ⁇ 15%.
- the total amount of alkali metal oxides is also limited.
- the amount range of R 2 O (R is an alkali metal) in composition is 1.5 ⁇ 20%.
- the amount range of R 2 O is preferably 2 ⁇ 17%.
- K 2 O has a higher effect of improving the devitrification resistance without greatly impairing the chemical durability as compared with the other alkali metal oxides. It is therefore particularly preferred to use K 2 O alone as an alkali metal oxide, in the amount range of 1.5 ⁇ 17% except for a special case where a low melting temperature is required.
- ZnO is an essential component for improving the chemical durability, inhibiting the thermal expansion coefficient from increasing and improving the melting properties.
- the amount range thereof in composition is therefore limited to 17 ⁇ 48%.
- the amount range of ZnO is preferably 25 ⁇ 45%, particularly preferably 27 ⁇ 42%.
- CuO is an essential component for absorbing near infrared light.
- the transmittance can be adjusted by incorporating at least 0.2%. However, when the amount thereof is greater than 12%, the crystallization tendency is intensified, and it is hence difficult to mass-produce the glass stably.
- the amount range of CuO in composition is therefore limited to 0.2 to 12%.
- the amount range of CuO is preferably 0.2 to 10%, particularly preferably 0.2 to 8%.
- As 2 O 3 is not an essential component, but it is a component effective for stably maintaining Cu 2+ and has an effect on improving the transmittance around 400 nm.
- the content of alkali metal oxides in composition is smaller than 12 mol %, it is preferred to incorporate As 2 O 3 .
- the content thereof is greater than 6 wt %, not only the crystallization tendency is intensified, but the glass is poor in chemical durability.
- the amount range of As 2 O 3 in composition is therefore limited to 0 ⁇ 6%, and it is particularly preferably 0.05 ⁇ 5%.
- B 2 O 3 may be incorporated up to 10% for improving the chemical durability. However, when the amount thereof exceeds 10%, not only no desired transmittance characteristic is obtained, but also the chemical durability reversely deteriorates.
- the amount range of B 2 O 3 in composition is therefore limited to 0 ⁇ 10%.
- the amount range of B 2 O 3 in composition is preferably 0 ⁇ 8%.
- Al 2 O 3 is a component for improving the chemical durability, and it may be incorporated up to 5%. When the amount thereof is greater than 5%, the crystallization tendency is intensified, and the glass shows poor melting properties.
- the amount range of Al 2 O 3 in composition is therefore limited to 0 ⁇ 5%.
- the amount range of Al 2 O 3 in composition is preferably 0.5 ⁇ 3%.
- MgO, CaO and SrO improve the chemical durability by incorporating them in a small amount.
- the amount range of MgO in composition is limited to 0 ⁇ 7%
- the amount range of CaO in composition is limited to.0 ⁇ 7%
- the amount range of SrO in composition is limited to 0 ⁇ 7%.
- the amount of each is preferably 0 ⁇ 5%.
- BaO has an effect on the improvement of devitrification resistance when incorporated in a small amount. However, when the amount thereof is greater than 12%, the glass shows poor melting properties.
- the amount range of BaO in composition is therefore limited to 0 ⁇ 12%, and it is preferably 0 ⁇ 8%.
- the above MgO, CaO, SrO and BaO belong to alkaline earth metal oxides, and the total amount of alkaline earth metal oxides is also essential in the near infrared absorption filter glass of the present invention.
- the amount range of R'O (R' is an alkaline earth metal) in composition is limited to 0 ⁇ 15%. The reason therefor is that when the amount of R'O is greater than 15%, the glass shows not only poor melting properties but poor chemical durability.
- the amount range of R'O in composition is preferably 0.5 ⁇ 10%.
- PbO has effects similar to those of ZnO, and ZnO may be replaced with PbO up to 25% of the composition.
- the effect of PbO on improving the chemical durability is lower than that of ZnO, and when the amount of PbO is more than 25%, the chemical durability intended in the present invention can be no longer obtained.
- the amount range of PbO in composition is therefore limited to 0 ⁇ 25%, and it is preferably 0 ⁇ 20%.
- Each of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Bi 2 O 3 improves the chemical durability when incorporated in a small amount.
- the amount of any one of La 2 O 3 , Y 2 O 3 and Gd 2 O 3 is greater than 3%, or when the amount of Bi 2 O 3 is greater than 5%, the crystallization tendency is intensified, and it is therefore difficult to stably produce the glass. Therefore, the amount rage of each of La 2 O 3 , Y 2 O 3 and Gd 2 O 3 in composition is limited to 0 ⁇ 3%, and the amount range of Bi 2 O 3 in composition is 0 ⁇ 5%.
- the amount rage of each of La 2 O 3 , Y 2 O 3 and Gd 2 O 3 is preferably 0 ⁇ 2%, and the amount range of Bi 2 O 3 is preferably 0 ⁇ 4%.
- In 2 O 3 improves the chemical durability in particular by incorporating it in a small amount. When the amount thereof is greater than 7%, the crystallization tendency is intensified.
- the amount range of In 2 O 3 in composition is therefore limited to 0 ⁇ 7%, and it is preferably 0 ⁇ 5%.
- Sc 2 O 3 Like In 2 O 3 , Sc 2 O 3 improves the chemical durability in particular by incorporating it in a small amount. When the amount thereof is greater than 5%, the crystallization tendency is intensified.
- the amount range of Sc 2 O 3 in composition is therefore limited to 0 ⁇ 5%, and it is preferably 0 ⁇ 4%.
- Components such as SiO 2 , TiO 2 , ZrO 2 , Nb 2 O 3 , Ta 2 O 5 , etc., are all for improving the chemical durability.
- SiO 2 , TiO 2 and ZrO 2 is greater than 3%, or when the amount of any one of Nb 2 O 5 and Ta 2 O 5 is greater than 7%, these are liable to remain when melted to form glass, so that it is required to increase the melting temperature, and as a result, it is difficult to stabilize Cu 2+ .
- the amount range of each of SiO 2 , TiO 2 and ZrO 2 in composition is limited to 0 ⁇ 3%
- the amount range of Nb 2 O 5 in composition is limited to 0 ⁇ 5%
- the amount range of Ta 2 O 5 in composition is limited to 0 to 7%.
- the amount range of each of SiO 2 , TiO 2 and ZrO 2 is preferably 0 ⁇ 2%
- the amount range of Nb 2 O 5 is preferably 0 ⁇ 3%
- the amount range of Ta 2 O 5 is preferably 0 ⁇ 5%.
- Ga 2 O 3 , GeO 2 and WO 3 are components for improving the chemical durability by incorporating them in a small amount.
- the amount of any one of Ga 2 O 3 and GeO 2 is greater than 3%, or when the amount of WO 3 is greater than 5%, the crystallization tendency is intensified. Therefore, the amount range of each of Ga 2 O 3 and GeO 2 in composition is limited to 0 ⁇ 3%, and the amount range of WO 3 in composition is limited to 0 ⁇ 5%.
- the amount range of each of Ga 2 O 3 and GeO 2 is preferably 0 ⁇ 2%, and the amount range of WO 3 is preferably 0 ⁇ 3%.
- high-valence metal oxides The above La 2 O 3 , Y 2 O 3 , Gd 2 O 3 , Bi 2 O 3 , In 2 O 3 , Sc 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , Nb 2 O 5 , Ta 2 O 5 , Ga 2 O 3 , GeO 2 and WO 3 will be generically referred to as high-valence metal oxides hereinafter.
- the total amount of the high-valence metal oxides is greater than 10%, not only the melting properties of the glass are deteriorated, but also the crystallization tendency is intensified.
- the total amount of the high-valence metal oxides is therefore preferably 0 ⁇ 10%.
- SnO is a component for improving the chemical durability of the glass.
- the amount range of SnO in composition is therefore limited to 0 ⁇ 5%, and it is preferably 0 ⁇ 3%.
- Sb 2 O 3 is a component for stabilizing Cu 2+ and improving the devitrification resistance. When the amount thereof is greater than 25%, the glass deteriorates in weatherability.
- the amount range of Sb 2 O 3 in composition is therefore limited to 0 ⁇ 25%, and it is preferably 0 to 15%.
- CeO 2 may be used as an agent for oxidizing CuO. When the amount thereof exceeds 2%, the glass deteriorates in transmittance characteristics in ultraviolet region.
- the amount range of CeO 2 in composition is therefore limited to 0 ⁇ 2%, and it is preferably 0 ⁇ 1%.
- F is a component effective for decreasing the melting temperature and obtaining stable coloring.
- the amount range thereof in which it neither intensifies the crystallization tendency nor increases the thermal expansion coefficient is up to 20%.
- the amount range thereof in composition is therefore limited to 0 ⁇ 20%, and it is preferably 0 ⁇ 15%.
- F may be fed by replacing part of oxides with fluoride.
- the near infrared absorption filter glass having the above composition has characteristic features that (a) it highly transmits light having a wavelength of 400 ⁇ 600 nm and sharply absorbs light having a wavelength larger than 600 nm, that (b) it has a small thermal expansion coefficient ( ⁇ 100-300 ) and causes almost no cracking when processed, and that (c) the difference between the haze values obtained before and after it is held in a relative humidity of 95% at 65° C. for 1,000 hours is small so that it has weatherability sufficient for use for a long period of time.
- Glass products having glass compositions shown in Tables 1 to 3 were prepared as follows.
- raw materials for glass components oxide itself, carbonate, nitrate, hydroxide, fluoride, phosphate, etc., were used.
- H 3 PO 4 , Al(OH) 3 , KNO 3 , BaCO 3 , CaCO 3 , ZnO, As 2 O 3 and CuO were used as raw materials.
- complex salts such as aluminum metaphosphate, zinc metaphosphate, etc.
- F may be added up to 20% without increasing the thermal expansion coefficient, and fluoride raw materials shall not be specially limited.
- the transmittance curve, the thermal expansion coefficient ( ⁇ 100-300 ), the Liquidus temperature (°C.) and the haze value difference (%) of the glass obtained in each of Examples 1 to 18 were determined by the following methods.
- thermomechanical analysis apparatus Measured for a thermal expansion coefficient at 100° ⁇ 300° C. with a thermomechanical analysis apparatus.
- the haze value difference was used as an index for the weatherability of glass.
- a mirror-polished sample having a thickness of 1 mm was prepared from a glass block, placed under accelerated testing conditions (maintained at a 65° C.--90% relative humidity for 1,000 hours), and measured for a haze value difference ⁇ H with a haze meter (%) (based on JIS standard: K6714) before and after the treatment to digitize the degree of deterioration of the glass surface.
- FIG. 1 shows the transmittance curves of the glass products obtained in Examples 3 and 4 as typical examples.
- the glass products obtained in Examples 1 to 18 had a thermal expansion coefficient ⁇ 100-300 of less than 130 to show that they were almost free from causing the problems of cracking or breaking, which takes place when glass is processed or polished.
- the glass products obtained in Examples 1 to 18 had a liquidus temperature of lower than 900° C. to show that they have devitrification resistance such that they can be stably mass-produced.
- the glass products obtained in Examples 1 to 18 had a haze value difference ⁇ H (%) of less than 2.5%, or had remarkably superior weatherability, to show that they retain stable performances for a long period of time under general use conditions of VTR cameras, etc.
- the glass obtained in Comparative Example 1 was glass whose glass components were included in the components of the present invention but whose P 2 O 5 content was 54.0% or exceeded the P 2 O 5 upper limit of 50% in the glass of the present invention.
- the glass obtained in Comparative Example 2 was glass whose glass components were included in the components of the present invention but whose alkali metal oxide R 2 O content was 23.0% or exceeded the R 2 O upper limit of 20% in the glass of the present invention.
- the glass obtained in Comparative Example 3 was phosphate-based glass described in Example 1 of JP-A-4-104981, which contained more than 60% of P 2 O 5 and contained a relatively large amount of Al 2 O 3 .
- Table 4 shows the detailed composition of the glass products obtained in these Comparative Examples 1 to 3.
- FIG. 1 shows the transmittance curve of the glass in Comparative Example 3 out of the glass products obtained in these Comparative Examples.
- Table 4 shows the thermal expansion coefficient ( ⁇ 100-300 ), the liquidus temperature and the haze value difference ⁇ H(%) of each of the glass products obtained in Comparative Examples 1 and 2. As is clearly shown in Table 4, there was obtained no product which satisfied both the low thermal expansion coefficient as an index for processability and the low haze value difference ⁇ H(%) as an index for weatherability. That is, the glass obtained in Comparative Example 1 had an ⁇ 100-300 of as low as 117 or had excellent processability, while it had a haze value difference ⁇ H of 85.0% or had enormous poor weatherability. The glass obtained in Comparative Example 2 had an ⁇ 100-300 of 145 and a have value difference ⁇ H of 90.0% and therefore it was inferior in both processability and weatherability.
- the near infrared absorption filter glass of the present invention has excellent transmittance characteristics in the ultraviolet region over conventional phosphate-based glass and has glass stability and processability which enable the mass production. Further, the near infrared absorption filter glass of the present invention has sufficient weatherability so that it can retain its performance as a color correction filter of a color VTR camera for a long period of time.
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Abstract
A near infrared absorption filter glass containing
______________________________________
P2 O5 35˜50%
Li2 O 0˜5%
Na2 O 0˜12%
K2 O 0˜20%
Cs2 O 0˜20%
R2 O (in which R is an alkali metal)
1.5˜20%
ZnO 17˜48%
MgO 0˜7%
CaO 0˜7%
SrO 0˜7%
BaO 0˜12%
R'O (in which R' is an alkaline earth metal)
0˜15%
CuO 0.2˜12%
______________________________________
in which % stands for % by weight
has excellent transmittance characteristics in the ultraviolet region over conventional phosphate-based glass, has glass stability and processability which enable the mass production, and further has sufficient weatherability.
Description
The present invention relates to near infrared absorption filter glass, more specifically to filter glass which has spectral characteristics that it highly transmits light having a wavelength of 400 to 600 nm and selectively absorbs near infrared light having a wavelength greater than about 600 nm, and which is used particularly for the color correction for a color VTR camera.
Infrared absorption filter glass has been studied in various ways and put to practical use. For example, JP-A-62-128943 discloses colored glass formed of 60˜90% by weight of P2 O5, 7.5˜20% by weight of Al2 O3, 0˜15% by weight of B2 O3 +SiO2, 1˜25% by weight of BaO+CaO+SrO, 0˜15% by weight of Y2 O3 +La2 O3 +ZrO2 +Ta2 O5 +TiO2, 0˜10% by weight of PbO and 0.4˜15.0% by weight of CuO.
Further, JP-A-4-104918 discloses phosphate glass formed of 60˜80% by weight of P2 O5, 3˜11% by weight of Al2 O3, 3˜9% by weight of BaO, 3˜20% by weight of MgO+CaO+BaO+SrO, 1˜5.5% by weight of Li2 O, 1˜10% by weight of Li2 O+Na2 O+K2 O, 0˜5% by weight of SiO2 +B2 O3, 0˜5% by weight of ZrO2 +TiO2 +Y2 O3 +La2 O3 and 0.2˜10% by weight of CuO.
Since, however, the glass disclosed in each of JP-A-62-128943 and JP-A-4-104918 contains a large amount of P2 O5, they are poor in chemical durability and difficult to use for a long period of time. Further, there is another problem that when a relatively large amount of Al2 O3 is incorporated for improving the chemical durability, the melting temperature increases, Cu2+ is consequently reduced and the transmittance around 400 nm is low due to Cu+ ion having absorption in an ultraviolet region.
The present inventors have made diligent studies to overcome the above problems, and as a result have found that, when it is attempted to obtain phosphate-based near infrared absorption glass containing CuO, there can be obtained glass which has high transmittance characteristics at 400˜600 nm and sharp absorption characteristics at a wavelength greater than 600 nm, useful as a near infrared absorption filter, and which has a small thermal expansion coefficient and excellent chemical durability, by adding a relatively large amount of ZnO and a proper amount of alkali metal oxides to a composition containing 35-50% of P2 O5.
The present invention has been made on the basis of the above finding, and the gist thereof is a near infrared absorption filter glass comprising
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P.sub.2 O.sub.5 35˜50%
Li.sub.2 O 0˜5%
Na.sub.2 O 0˜12%
K.sub.2 O 0˜20%
Cs.sub.2 O 0˜20%
R.sub.2 O (in which R is an alkali metal)
1.5˜20%
ZnO 17˜48%
MgO 0˜7%
CaO 0˜7%
SrO 0˜7%
BaO 0˜12%
R'O (in which R' is an alkaline earth metal)
0˜15%
CuO 0.2˜12%
in which % stands for % by weight.
______________________________________
FIG. 1 shows transmittance curves of glass obtained in Examples 3 and 4 and Comparative Example 3.
The near infrared absorption filter glass of the present invention comprises 35˜50% of P2 O5, 0˜5% of Li2 O, 0˜12% of Na2 O, 0˜20% of K2 O, 0˜20% of Cs2 O, 1.5˜20% of R2 O (in which R is an alkali metal), 17˜48% of ZnO and 0.2˜12% of CuO.
The reason for the limitation of the amount of each component in composition to the above numerical range is as follows.
In the near infrared absorption filter glass of the present invention, P2 O5 is the most preferred glass network-forming component for increasing the transmittance at 400˜600 nm and sharply changing the absorption by Cu2+ in a wavelength region greater than 700 nm. When the content thereof is less than 35%, no desired transmittance characteristic is obtained, and further, it is difficult to stably produce the glass since the crystallization tendency of the glass increases. When the above content exceeds 50%, the glass shows a sharp decrease in chemical durability, and the glass intended in the present invention is no longer obtained. Therefore, the amount range of P2 O5 in composition is limited to 35˜50%. The amount range of P2 O5 is preferably 37˜49%, particularly preferably 40˜48%.
In the near infrared absorption filter glass of the present invention, K2 O is a component for improving devitrification resistance and improving the melting properties of glass. When the amount thereof is greater than 20%, the glass is poor in chemical durability and has an increased thermal expansion coefficient. The amount range of K2 O in composition is therefore limited to 0˜20%, and it is preferably 0˜17%.
The near infrared absorption filter glass of the present invention may contain Li2 O, Na2 O and Cs2 O as alkali metal oxides as required in addition to the above K2 O.
Li2 O, Na2 O and Cs2 O are components for improving the melting properties of the glass and improving devitrification resistance. When the amounts of these components exceed 5%, 12% or 20%, the glass is poor in chemical durability, or the crystallization tendency is intensified. Therefore, the amount range of Li2 O in composition is limited to 0˜5%, the amount range of Na2 O in composition is limited to 0˜12%, and the amount range of Cs2 O in composition is limited to 0˜20%. The amount range of Li2 O is preferably 0˜3%, the amount range of Na2 O is preferably 0˜8%, particularly preferably 0˜6%, and the amount range of Cs2 O is preferably 0˜17%, particularly preferably 0˜15%.
In the near infrared absorption filter glass of the present invention, the total amount of alkali metal oxides is also limited. The amount range of R2 O (R is an alkali metal) in composition is 1.5˜20%. When the amount of R2 O is less than 1.5%, the crystallization tendency increases. On the other hand, when the above amount exceeds 20%, the glass is poor in chemical durability and has an increased thermal expansion coefficient. The amount range of R2 O is preferably 2˜17%.
In the near infrared absorption filter glass of the present invention, K2 O has a higher effect of improving the devitrification resistance without greatly impairing the chemical durability as compared with the other alkali metal oxides. It is therefore particularly preferred to use K2 O alone as an alkali metal oxide, in the amount range of 1.5˜17% except for a special case where a low melting temperature is required.
In the near infrared absorption filter glass of the present invention, ZnO is an essential component for improving the chemical durability, inhibiting the thermal expansion coefficient from increasing and improving the melting properties. When the amount of ZnO is less than 17%, these effects cannot be produced. On the other hand, when the above amount exceeds 48%, the crystallization tendency is intensified, and it is liable to be difficult to stably produce the glass. The amount range thereof in composition is therefore limited to 17˜48%. The amount range of ZnO is preferably 25˜45%, particularly preferably 27˜42%.
In the near infrared absorption filter glass of the present invention, CuO is an essential component for absorbing near infrared light. The transmittance can be adjusted by incorporating at least 0.2%. However, when the amount thereof is greater than 12%, the crystallization tendency is intensified, and it is hence difficult to mass-produce the glass stably. The amount range of CuO in composition is therefore limited to 0.2 to 12%. The amount range of CuO is preferably 0.2 to 10%, particularly preferably 0.2 to 8%.
In the near infrared absorption filter glass of the present invention, As2 O3 is not an essential component, but it is a component effective for stably maintaining Cu2+ and has an effect on improving the transmittance around 400 nm. In particular, when the content of alkali metal oxides in composition is smaller than 12 mol %, it is preferred to incorporate As2 O3. When the content thereof is greater than 6 wt %, not only the crystallization tendency is intensified, but the glass is poor in chemical durability. The amount range of As2 O3 in composition is therefore limited to 0˜6%, and it is particularly preferably 0.05˜5%.
B2 O3 may be incorporated up to 10% for improving the chemical durability. However, when the amount thereof exceeds 10%, not only no desired transmittance characteristic is obtained, but also the chemical durability reversely deteriorates. The amount range of B2 O3 in composition is therefore limited to 0˜10%. The amount range of B2 O3 in composition is preferably 0˜8%.
Al2 O3 is a component for improving the chemical durability, and it may be incorporated up to 5%. When the amount thereof is greater than 5%, the crystallization tendency is intensified, and the glass shows poor melting properties. The amount range of Al2 O3 in composition is therefore limited to 0˜5%. The amount range of Al2 O3 in composition is preferably 0.5˜3%.
MgO, CaO and SrO improve the chemical durability by incorporating them in a small amount. However, when the amount of each is greater than 7%, the glass deteriorate in melting properties and devitrification. Therefore, the amount range of MgO in composition is limited to 0˜7%, the amount range of CaO in composition is limited to.0˜7%, and the amount range of SrO in composition is limited to 0˜7%. The amount of each is preferably 0˜5%.
BaO has an effect on the improvement of devitrification resistance when incorporated in a small amount. However, when the amount thereof is greater than 12%, the glass shows poor melting properties. The amount range of BaO in composition is therefore limited to 0˜12%, and it is preferably 0˜8%.
The above MgO, CaO, SrO and BaO belong to alkaline earth metal oxides, and the total amount of alkaline earth metal oxides is also essential in the near infrared absorption filter glass of the present invention. The amount range of R'O (R' is an alkaline earth metal) in composition is limited to 0˜15%. The reason therefor is that when the amount of R'O is greater than 15%, the glass shows not only poor melting properties but poor chemical durability. The amount range of R'O in composition is preferably 0.5˜10%.
PbO has effects similar to those of ZnO, and ZnO may be replaced with PbO up to 25% of the composition. However, the effect of PbO on improving the chemical durability is lower than that of ZnO, and when the amount of PbO is more than 25%, the chemical durability intended in the present invention can be no longer obtained. The amount range of PbO in composition is therefore limited to 0˜25%, and it is preferably 0˜20%.
Each of La2 O3, Y2 O3, Gd2 O3 and Bi2 O3 improves the chemical durability when incorporated in a small amount. However, when the amount of any one of La2 O3, Y2 O3 and Gd2 O3 is greater than 3%, or when the amount of Bi2 O3 is greater than 5%, the crystallization tendency is intensified, and it is therefore difficult to stably produce the glass. Therefore, the amount rage of each of La2 O3, Y2 O3 and Gd2 O3 in composition is limited to 0˜3%, and the amount range of Bi2 O3 in composition is 0˜5%. The amount rage of each of La2 O3, Y2 O3 and Gd2 O3 is preferably 0˜2%, and the amount range of Bi2 O3 is preferably 0˜4%.
In2 O3 improves the chemical durability in particular by incorporating it in a small amount. When the amount thereof is greater than 7%, the crystallization tendency is intensified. The amount range of In2 O3 in composition is therefore limited to 0˜7%, and it is preferably 0˜5%.
Like In2 O3, Sc2 O3 improves the chemical durability in particular by incorporating it in a small amount. When the amount thereof is greater than 5%, the crystallization tendency is intensified. The amount range of Sc2 O3 in composition is therefore limited to 0˜5%, and it is preferably 0˜4%.
Components such as SiO2, TiO2, ZrO2, Nb2 O3, Ta2 O5, etc., are all for improving the chemical durability. When the amount of any one of SiO2, TiO2 and ZrO2 is greater than 3%, or when the amount of any one of Nb2 O5 and Ta2 O5 is greater than 7%, these are liable to remain when melted to form glass, so that it is required to increase the melting temperature, and as a result, it is difficult to stabilize Cu2+. Therefore, the amount range of each of SiO2, TiO2 and ZrO2 in composition is limited to 0˜3%, the amount range of Nb2 O5 in composition is limited to 0˜5%, and the amount range of Ta2 O5 in composition is limited to 0 to 7%. The amount range of each of SiO2, TiO2 and ZrO2 is preferably 0˜2%, the amount range of Nb2 O5 is preferably 0˜3%, and the amount range of Ta2 O5 is preferably 0˜5%.
Ga2 O3, GeO2 and WO3 are components for improving the chemical durability by incorporating them in a small amount. When the amount of any one of Ga2 O3 and GeO2 is greater than 3%, or when the amount of WO3 is greater than 5%, the crystallization tendency is intensified. Therefore, the amount range of each of Ga2 O3 and GeO2 in composition is limited to 0˜3%, and the amount range of WO3 in composition is limited to 0˜5%. The amount range of each of Ga2 O3 and GeO2 is preferably 0˜2%, and the amount range of WO3 is preferably 0˜3%.
The above La2 O3, Y2 O3, Gd2 O3, Bi2 O3, In2 O3, Sc2 O3, SiO2, TiO2, ZrO2, Nb2 O5, Ta2 O5, Ga2 O3, GeO2 and WO3 will be generically referred to as high-valence metal oxides hereinafter. When the total amount of the high-valence metal oxides is greater than 10%, not only the melting properties of the glass are deteriorated, but also the crystallization tendency is intensified. The total amount of the high-valence metal oxides is therefore preferably 0˜10%.
SnO is a component for improving the chemical durability of the glass. When the amount thereof is greater than 5%, the glass deteriorates in transmittance characteristic, and the crystallization tendency is intensified. The amount range of SnO in composition is therefore limited to 0˜5%, and it is preferably 0˜3%.
Sb2 O3 is a component for stabilizing Cu2+ and improving the devitrification resistance. When the amount thereof is greater than 25%, the glass deteriorates in weatherability. The amount range of Sb2 O3 in composition is therefore limited to 0˜25%, and it is preferably 0 to 15%.
CeO2 may be used as an agent for oxidizing CuO. When the amount thereof exceeds 2%, the glass deteriorates in transmittance characteristics in ultraviolet region. The amount range of CeO2 in composition is therefore limited to 0˜2%, and it is preferably 0˜1%.
Further, F is a component effective for decreasing the melting temperature and obtaining stable coloring. The amount range thereof in which it neither intensifies the crystallization tendency nor increases the thermal expansion coefficient is up to 20%. The amount range thereof in composition is therefore limited to 0˜20%, and it is preferably 0˜15%. F may be fed by replacing part of oxides with fluoride.
The near infrared absorption filter glass having the above composition, provided by the present invention, has characteristic features that (a) it highly transmits light having a wavelength of 400˜600 nm and sharply absorbs light having a wavelength larger than 600 nm, that (b) it has a small thermal expansion coefficient (α100-300) and causes almost no cracking when processed, and that (c) the difference between the haze values obtained before and after it is held in a relative humidity of 95% at 65° C. for 1,000 hours is small so that it has weatherability sufficient for use for a long period of time.
Examples of the present invention will be explained hereinafter.
Glass products having glass compositions shown in Tables 1 to 3 were prepared as follows.
As raw materials for glass components, oxide itself, carbonate, nitrate, hydroxide, fluoride, phosphate, etc., were used. For glass of Example 3 for example, H3 PO4, Al(OH)3, KNO3, BaCO3, CaCO3, ZnO, As2 O3 and CuO were used as raw materials. Further, there shall be no limitation to be imposed on the use of complex salts such as aluminum metaphosphate, zinc metaphosphate, etc., as raw materials. Moreover, F may be added up to 20% without increasing the thermal expansion coefficient, and fluoride raw materials shall not be specially limited.
A batch of the above raw materials was well mixed, melted in a platinum crucible at 900°˜1,250° C., stirred, defoamed, homogenized, cast into a pre-heated mold and gradually cooled to give glass in the form of a block in each of Examples 1 to 18. Tables 1 to 3 show the glass compositions obtained in Examples 1 to 18.
The transmittance curve, the thermal expansion coefficient (α100-300), the Liquidus temperature (°C.) and the haze value difference (%) of the glass obtained in each of Examples 1 to 18 were determined by the following methods.
(1) Transmittance Curve
Measured with a Shimadzu spectrophotometer UV3101-PC.
(2) Thermal Expansion Coefficient (α100-300)
Measured for a thermal expansion coefficient at 100°˜300° C. with a thermomechanical analysis apparatus.
(3) Liquidus Temperature (°C.)
Maintained in a temperature-gradient furnace for 30 minutes and determined by the observation through a microscope for crystals.
(4) Haze Value Difference (%)
In the present invention, the haze value difference was used as an index for the weatherability of glass. A mirror-polished sample having a thickness of 1 mm was prepared from a glass block, placed under accelerated testing conditions (maintained at a 65° C.--90% relative humidity for 1,000 hours), and measured for a haze value difference ΔH with a haze meter (%) (based on JIS standard: K6714) before and after the treatment to digitize the degree of deterioration of the glass surface.
The above haze values (H) were determined on the basis of the following equation.
H=Td/Tt×100 (%)
Tt: Total light transmittance (%)
Td: Diffusion transmittance (%)
The samples were measured for transmittance curves to show that the glass products obtained in Examples 1 to 18 highly transmitted light having a wavelength of 400˜600 nm and sharply absorbed light having a wavelength of greater than 600 nm so that they were suitable as near infrared absorption filter glass. FIG. 1 shows the transmittance curves of the glass products obtained in Examples 3 and 4 as typical examples.
As shown in Tables 1 to 3, further, the glass products obtained in Examples 1 to 18 had a thermal expansion coefficient α100-300 of less than 130 to show that they were almost free from causing the problems of cracking or breaking, which takes place when glass is processed or polished.
As shown in Tables 1 to 3, further, the glass products obtained in Examples 1 to 18 had a liquidus temperature of lower than 900° C. to show that they have devitrification resistance such that they can be stably mass-produced.
As shown in Tables 1 to 3, further, the glass products obtained in Examples 1 to 18 had a haze value difference ΔH (%) of less than 2.5%, or had remarkably superior weatherability, to show that they retain stable performances for a long period of time under general use conditions of VTR cameras, etc.
TABLE 1
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No.
Example
Component 1 2 3 4 5 6
__________________________________________________________________________
P2O5 48.0
41.0 44.0
45.0 45.0
45.0
B2O3 4.0
Al2O3 2.0 1.0 2.0 1.0 2.0
Li2O 1.0
Na2O 3.0
K2O 6.0 7.5 9.0 7.0 9.0 8.5
Cs2O 1.0 2.0
R2O* 10.0
8.5 9.0 7.0 9.0 10.5
MgO 1.0 1.0
CaO 2.0 2.0 2.0 0.5
SrO 2.0
BaO 2.5 5.0 3.0 2.0 4.0 3.0
R'O** 2.5 7.0 5.0 7.0 5.0 3.5
ZnO 33.5
35.5 37.0
30.5 28.0
35.0
PbO 7.0
As2O3 1.0 1.0 1.0 2.0 1.0 0.5
La2O3 0.5
Y2O3 1.0
Gd2O3
Bi2O3
In2O3 2.0
Sc2O3
Ga2O3
GeO2
SiO2
TiO2 2.0
ZrO2
Nb2O5
Ta2O5
WO3
High-valence
0 1.0 0 0 0 4.5
metal oxide
SnO 1.0
Sb2O3 0.5
CeO2
CuO 2.0 1.0 2.0 7.5 2.5 1.0
Total 100.0
100.0
100.0
100.0
100.0
100.0
F content 0.0 0.0 0.0 0.0 0.0 0.0
α100˜300
119 107 108 103 114 106
Liquidus Temp. (°C.)
700 780 760 835 790 840
Haze value (%)
0.6 0.7 0.4 1.2 0.5 1.1
__________________________________________________________________________
*R2O: Li2O + Na2O + K2O + Li2O
**R'O: MgO + CaO + SrO + BaO
TABLE 2
__________________________________________________________________________
No.
Example
Component 7 8 9 10 11 12
__________________________________________________________________________
P2O5 45.0
47.0 44.0
44.0 39.0
44.0
B2O3 6.0
Al2O3 1.0 2.0 2.0 1.0 1.0
Li2O
Na2O 2.0
K2O 10.5
7.0 9.0 9.0 6.0 16.0
Cs2O
R2O* 10.5
9.0 9.0 9.0 6.0 16.0
MgO 1.0
CaO 2.0 2.0 2.0 2.0 2.0
SrO 1.0 2.0
BaO 2.0 3.0 3.0 3.0 5.0 3.0
R'O** 4.0 7.0 5.0 5.0 7.0 5.0
ZnO 35.0
31.0 34.0
34.0 36.5
30.0
PbO
As2O3 0.5 1.0 1.0 1.0 1.0 0.0
La2O3
Y2O3
Gd2O3 2.0
Bi2O3 3.0
In2O3 2.0
Sc2O3 2.0 1.5
Ga2O3 2.0
GeO2 1.0
SiO2
TiO2
ZrO2 1.0
Nb2O5 1.0
Ta2O5 1.0
WO3
High-valence
4.0 2.0 3.0 3.0 2.5 2.0
metal oxide
SnO
Sb2O3
CeO2
CuO 1.0 2.0 2.0 2.0 1.0 2.0
Total 100.0
100.0
100.0
100.0
100.0
100.0
F content 0.0 0.0 0.0 0.0 0.0 0.0
α100˜300
103 109 111 107 99 129
Liquidus Temp. (°C.)
845 850 770 840 850 820
Haze value (%)
0.2 1.1 0.4 0.3 1.0 2.1
__________________________________________________________________________
*R2O: Li2O + Na2O + K2O + Li2O
**R'O: MgO + CaO + SrO + BaO
TABLE 3
__________________________________________________________________________
No.
Example
Component 13 14 15 16 17 18
__________________________________________________________________________
P2O5 42.8
49.0
44.0
45.0
44.7 42.0
B2O3 2.0
Al2O3 1.0 3.0 2.0 1.0 0.5
Li2O 2.0 LiF: 4.3
Na2O 7.0 1.0
K2O 6.7 3.0 8.0 2.0 K2O:1.5 KF:3.5
Cs2O 14.0
R2O* 6.7 5.0 8.0 9.0 1.5 15.0
MgO
CaO 2.0 2.0 CaF2:2.0
SrO 1.0 SrF2:1.0
3.0
BaO 5.2 3.0 BaF2:3.0
6.8
R'O** 8.2 0 5.0 0 0 9.8
ZnO 24.3
31.0
20.0
44.0
ZnO:18 ZnF2:20
30.0
PbO 18.0 7.0
As2O3 0.5 2.0 1.0 0.0 1.0 0.2
La2O3
Y2O3
Gd2O3
Bi2O3
In2O3
Sc2O3 2.0
Ga2O3
GeO2
SiO2 0.5
TiO2
ZrO2
Nb2O5
Ta2O5
WO3 3.0
High-valence
0 5.5 0 0 0 0
metal oxide
SnO
Sb2O3 15.0
CeO2 0.5
CuO 1.5 4.0 2.0 1.0 1.0 0.5
Total 100.0
100.0
100.0
100.0
100.0 100.0
F content 0.0 0.0 0.0 0.0 0.0 0.0
α100˜300
120 98 102 118 128 110
Liquidus Temp. (°C.)
750 860 760 680 700 810
Haze value (%)
0.8 1.2 1.5 1.7 1.5 1.9
__________________________________________________________________________
*R2O: Li2O + Na2O + K2O + Li2O
**R'O: MgO + CaO + SrO + BaO
The glass obtained in Comparative Example 1 was glass whose glass components were included in the components of the present invention but whose P2 O5 content was 54.0% or exceeded the P2 O5 upper limit of 50% in the glass of the present invention.
The glass obtained in Comparative Example 2 was glass whose glass components were included in the components of the present invention but whose alkali metal oxide R2 O content was 23.0% or exceeded the R2 O upper limit of 20% in the glass of the present invention.
The glass obtained in Comparative Example 3 was phosphate-based glass described in Example 1 of JP-A-4-104981, which contained more than 60% of P2 O5 and contained a relatively large amount of Al2 O3.
Table 4 shows the detailed composition of the glass products obtained in these Comparative Examples 1 to 3.
FIG. 1 shows the transmittance curve of the glass in Comparative Example 3 out of the glass products obtained in these Comparative Examples.
As is clearly shown in FIG. 1, when the transmittance of the glass obtained in Comparative Example 3 and the transmittance of the glass obtained in Example 3 at wavelengths of 500 nm and 700 nm are overlapped, the transmittance of the glass obtained in Comparative Example 3 around 400 nm is lower. In the weatherability test, the glass obtained in Comparative Example 3 was maintained under a 65° C.--90% relatively humidity to show a haze value of 91.5%, and it is seen that the glass obtained in Comparative Example 3 has a problem on the reliability in a long-term use. That is, the glass obtained in Comparative Example 3 was notably inferior to the glass of the present invention in respect of transmittance characteristics and weatherability.
Table 4 shows the thermal expansion coefficient (α100-300), the liquidus temperature and the haze value difference ΔH(%) of each of the glass products obtained in Comparative Examples 1 and 2. As is clearly shown in Table 4, there was obtained no product which satisfied both the low thermal expansion coefficient as an index for processability and the low haze value difference ΔH(%) as an index for weatherability. That is, the glass obtained in Comparative Example 1 had an α100-300 of as low as 117 or had excellent processability, while it had a haze value difference ΔH of 85.0% or had immensely poor weatherability. The glass obtained in Comparative Example 2 had an α100-300 of 145 and a have value difference ΔH of 90.0% and therefore it was inferior in both processability and weatherability.
TABLE 4
______________________________________
No.
Comparative Example
Component 1 2 3
______________________________________
P2O5 54.0 46.0 71.8
B2O3 0.5
Al2O3 1.0 4.7
Li2O 1.0 5.0
Na2O 2.0 6.0
K2O 9.0 16.0
Cs2O
R2O* 11.0 23.0
MgO 4.8
CaO 2.0
SrO 1.0
BaO 7.0 3.0 8.9
R'O** 8.0 5.0 13.7
ZnO 23.0 27.0
PbO
As2O3 1.5 1.0 0.0
La2O3
Y2O3
Gd2O3
Bi2O3
In2O3
Sc2O3
Ga2O3
GeO2
SiO2
TiO2
ZrO2
Nb2O5
Ta2O5
WO3
High-valence 0 0 0
metal oxide
SnO
Sb2O3
CeO2
CuO 1.5 2.0 4.3
Total 100.0 100.0 100.00
F content 0.0 0.0 0.0
α100˜300
117 145 118
Liquidus Temp. (°C.)
680 660 850
Haze value (%) 85.0 90.0 91.5
______________________________________
*R2O: Li2O + Na2O + K2O + Li2O
**R'O: MgO + CaO + SrO + BaO
As explained above, the near infrared absorption filter glass of the present invention has excellent transmittance characteristics in the ultraviolet region over conventional phosphate-based glass and has glass stability and processability which enable the mass production. Further, the near infrared absorption filter glass of the present invention has sufficient weatherability so that it can retain its performance as a color correction filter of a color VTR camera for a long period of time.
Claims (8)
1. A near infrared absorption filter glass comprising
______________________________________
P.sub.2 O.sub.5 35˜50%
Li.sub.2 O 0˜5%
Na.sub.2 O 0˜12%
K.sub.2 O 0˜20%
Cs.sub.2 O 0˜20%
R.sub.2 O (in which R is an alkali metal)
1.5˜20%
ZnO 17˜48%
MgO 0˜7%
CaO 0˜7%
SrO 0˜7%
BaO 0˜12%
R'O (in which R' is an alkaline earth metal)
0˜15%
CuO 0.2˜12%
______________________________________
in which % stands for % by weight.
2. The near infrared absorption filter glass of claim 1, wherein the near infrared absorption filter glass contains
______________________________________
P.sub.2 O.sub.5 37˜49%
Li.sub.2 O 0˜3%
Na.sub.2 O 0˜8%
K.sub.2 O 0˜17%
Cs.sub.2 O 0˜17%
R.sub.2 O (in which R is an alkali metal)
2˜17%
ZnO 25˜45%
MgO 0˜5%
CaO 0˜5%
SrO 0˜5%
BaO 0˜8%
R'O (in which R' is an alkaline earth metal)
0.5˜10%
CuO 0.2˜10%
in which % stands for % by weight.
______________________________________
3. The near infrared absorption filter glass of claim 1, wherein the near infrared absorption filter glass contains
______________________________________
P.sub.2 O.sub.5 40˜48%
Li.sub.2 O 0˜3%
Na.sub.2 O 0˜6%
K.sub.2 O 0˜17%
Cs.sub.2 O 0˜15%
R.sub.2 O (in which R is an alkali metal)
2˜17%
ZnO 27˜42%
MgO 0˜5%
CaO 0˜5%
SrO 0˜5%
BaO 0˜8%
R'O (in which R' is an alkaline earth metal)
0.5˜10%
CuO 0.2˜10%
in which % stands for % by weight.
______________________________________
4. The near infrared absorption filter glass of any one of claim 1, wherein the near infrared absorption filter glass contains 0.05 to 5% by weight of As2 O3.
5. The near infrared absorption filter glass of any one of claim 1, wherein the near infrared absorption filter glass contains, as arbitrary components,
______________________________________ B.sub.2 O.sub.3 0-10% Al.sub.2 O.sub.3 0-5% PbO 0-25% La.sub.2 O.sub.3 0-3% Y.sub.2 O.sub.3 0-3% Gd.sub.2 O.sub.1 0-3% Bi.sub.2 O.sub.3 0-5% In.sub.2 O.sub.3 0-7% Sc.sub.2 O.sub.3 0-5% SiO.sub.2 0-3% TiO.sub.2 0-3% ZrO.sub.2 0-3% Nb.sub.2 O.sub.5 0-5% Ta.sub.2 O.sub.5 0-7% Ga.sub.2 O.sub.3 0-3% GeO.sub.2 0-3% WO.sub.3 0-5% SnO 0-5% Sb.sub.2 O.sub.3 0-25% CeO.sub.2 0-2% F 0-20% in which % stands for % by weight. ______________________________________
6. The near infrared absorption filter glass of any one of claim 1, wherein the near infrared absorption filter glass contains
Al.sub.2 O.sub.3 0.5˜3%.
7. The near infrared absorption filter glass of any one of claim 1, wherein the near infrared absorption filter glass contains K2 O alone as the alkali metal oxide R2 O and its amount range is 1.5˜17%.
8. The near infrared absorption filter glass of any one of claim 1, wherein the near infrared absorption filter glass has a thermal expansion coefficient α100-300 of 130×10-7 /°C. or less, and the near infrared absorption filter glass shows a haze value difference (%) of 2.5% or less when measured before and after the near infrared absorption filter glass is maintained at a relative humidity of 90% at 64° C. for 1,000 hours.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-186886 | 1995-07-24 | ||
| JP18688695 | 1995-07-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5668066A true US5668066A (en) | 1997-09-16 |
Family
ID=16196411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/685,572 Expired - Fee Related US5668066A (en) | 1995-07-24 | 1996-07-24 | Near infrared absorption filter glass |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US5668066A (en) |
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